CN104175686A - Preparation method of polytetrafluoroethylene (PTFE) composite dielectric substrate - Google Patents
Preparation method of polytetrafluoroethylene (PTFE) composite dielectric substrate Download PDFInfo
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Abstract
The invention relates to the field of a high-frequency copper-clad plate of a polytetrafluoroethylene (PTFE) dielectric substrate, and in particular relates to a preparation method of a polytetrafluoroethylene (PTFE) composite dielectric substrate used for a microwave circuit. The method comprises the steps of firstly, mixing fluororesin emulsion, inorganic filler and a thickening agent to prepare stable and uniform dispersion liquid; after that, enabling a release type base material to be coated with the dispersion liquid, and then baking; after baking, carrying out release type separation on a resin layer and the base material; cutting and overlapping the separated resin layer according to the thickness and the size of the substrate; covering the two sides of the resin layer with copper foils, and carrying out high-temperature lamination sintering to obtain the PTFE composite dielectric substrate covered by the copper foils at the double sides. After the preparation method is used, the formation of a hole in the composite dielectric substrate and the residue of an organic auxiliary agent are effectively reduced; the preparation method has the advantages of being simple and convenient in technology, beneficial to large scale production, etc.
Description
Technical field
The present invention relates to PTFE medium substrate high-frequency copper-clad plate field, relate in particular to the preparation method of circuit PTFE composite medium substrate for a kind of microwave.
Background technology
Along with electronics and IT products are gradually towards high frequency, high speed future development.Traditional FR-4 baseplate material will be replaced by high speed, high frequency and high reliability baseplate material gradually.In recent years, scientific worker conducts in-depth research selection and the performance of high frequency, high speed baseplate material, is intended to find the good baseplate material of dielectric properties, mechanical property and thermal property, to meet the requirement of actual use.
Polytetrafluoroethylene (PTFE) (PTFE) is since the commercialization of 1945 Nian You E.I.Du Pont Company is produced, physical property and chemical property due to this material uniqueness, people constantly open up this material in the application of every field, result of study shows, polytetrafluoroethylene (PTFE) has good electric property, resistance to chemical attack, heat-resisting, serviceability temperature scope is wide, water imbibition is low, in high-frequency range, dielectric constant, dielectric loss factor change seldom, are highly suitable for the matrix resin as high-speed digitization and high frequency substrate material.Utilize the dielectric properties (low-k and low dielectric loss) of PTFE material excellence to manufacture the copper-clad plate of frequency applications existing historical for many years.
PTFE copper-clad plate can simply be divided into two classes, and the one, conventional glass-fiber-fabric enhancement mode PTFE copper-clad plate, it is to manufacture by the technique of PTFE emulsion dipping glass-fiber-fabric, the 2nd, the composite medium substrate strengthening without glass-fiber-fabric, it needs the processing technology of relative complex.
US Patent No. 4335180 has been introduced a kind of preparation method without glass-fiber-fabric enhancement mode PTFE copper-clad plate: by fluorine-containing resin emulsion, the mixing such as filler, stir, then add flocculating agent, make fluorinated resin particle, filler and fiber etc. are condensed into dough/pasta shape (dough-like) object, this object is filtered, dry process (160 ℃/24h), obtain the mixture (chunk) of fragment shape, again lubricant is joined in this broken flaky mixture, be uniformly mixed fully, and by extruding, the operations such as calendering are made certain thickness sheet material, this sheet material toasts (246 ℃/24h) again, cover again afterwards Copper Foil, carry out lamination, obtain having the PTFE copper-clad plate of high filler content.This method can produce a large amount of waste water, complex process, and manufacturing cost is high; And after lubricant is dried, substrate inside can exist more cavity, cause the water absorption rate of sheet material large.
Chinese patent 201310025072.7 has been introduced a kind of preparation method of PTFE copper-clad plate of high filler content: first fluororesin powder is mixed with inorganic filler, then add organic lubricant, stir into face bulk object, extrude again, the operation such as calendering, obtain sheet material, this sheet material is carried out to heat (250 ℃/6h) and process, then flood this sheet material with fluororesin dispersion emulsion, and be dried, bake and bank up with earth, sintering, obtain the sheet material that hole is few, one deck resin molding has been covered on surface.Although this method can reduce space and the water absorption rate of substrate, exist equally technological process complicated, the shortcomings such as manufacturing cost height.
In the preparation method of the existing PTFE composite medium substrate without reinforcing material, all exist technological process complicated, inefficient defect, and in fluoro-resin emulsion, exist multiple organic additive, remove in the process of organic additive, generally all need long-time (more than 4h) high temperature (more than 200 ℃) to process, especially in containing filler systems, after high-temperature baking, the resin combination reunion of easily luming, even if the long-time baking of high temperature can not guarantee organic additive and moisture and remove completely, in addition, organic additive and moisture residual very large to the performance impact of substrate, especially dielectric properties.
Therefore, find a kind of simple process, efficiency is high and the preparation method of the PTFE composite medium substrate excellent combination property that makes to make is current problem demanding prompt solution.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of PTFE composite medium substrate, particularly the preparation method of circuit PTFE composite medium substrate for a kind of microwave.
In order to reach this goal of the invention, the present invention has adopted following technical scheme:
First aspect, the invention provides the preparation method of PTFE composite medium substrate for a kind of microwave circuit, comprises the steps:
(1) fluoro-resin emulsion, inorganic filler are proportionally carried out to mixed at high speed, prepare fluororesin dispersion liquid, adjust the viscosity of dispersion liquid at 100mPa.s-850mPa.s; (2) by dispersion liquid step (1) Suo Shu with coating equipment be coated in can be release base material on, obtain the base material of resinizing of even thickness;
(3) base material of resinizing step (2) Suo Shu is toasted, after baking, resin bed and base material are carried out release separatedly, obtain the resin bed of even thickness;
(4) by resin bed step (3) Suo Shu according to the thickness of substrate and size, carry out cutting and superimposed, then on the two sides of resin bed, cover Copper Foil and carry out high temperature lamination sintering, can obtain the PTFE composite medium substrate of two-sided copper foil covered.
The fluoro-resin emulsion that step of the present invention (1) is described and the ratio of inorganic filler can be adjusted as required, for example fluoro-resin emulsion weight portion accounts for the 10%-90% (in organic solid content) of fluoro-resin emulsion and inorganic filler total amount, and the content of thickener is the 05-5.0% of fluoro-resin emulsion total amount.
As optimal technical scheme, the viscosity of the described dispersion liquid of step of the present invention (1) is at 150mPa.s-850mPa.s, can be for example 150mPa.s, 170mPa.s, 200mPa.s, 250mPa.s, 300mPa.s, 350mPa.s, 420mPa.s, 550mPa.s, 600mPa.s, 650mPa.s, 700mPa.s, 850mPa.s, be preferably 300mPa.s-600mPa.s.
In preparation method of the present invention, the viscosity of dispersion liquid is very big on the impact of copper-clad plate, resin layer thickness that the viscosity of glue is too high or too low all can cause applying time is inhomogeneous, thereby have influence on the performance of copper-clad plate, especially breakdown voltage is had the greatest impact, the present invention adopts the viscosity of above-mentioned dispersion liquid, and in the time of can realizing coating, resin layer thickness is even, thereby makes the PTFE composite medium substrate of excellent combination property.
As optimal technical scheme, step (1) is adjusted the viscosity of dispersion liquid by adding thickener.
Preferably, described thickener is the mixture of any one or at least two kinds in polyoxyethylene groups distyrene phenyl ether, neopelex, NPE, lauryl sodium sulfate or poly dimethyl silane, is preferably polyoxyethylene groups distyrene phenyl ether or NPE.
Thickener of the present invention has that addition is few and thickening effect is obvious, does not affect the performance of complex media, and is easily removed in follow-up bake process.As optimal technical scheme, the described fluoro-resin emulsion of step of the present invention (1) is the mixture of any one or at least two kinds in polyflon emulsion, tetrafluoroethene-perfluorinated alkoxy vinyl ether resin emulsion or fluorinated ethylene propylene copolymer resin emulsion, is preferably polyflon emulsion.
Preferably, the particle diameter of described fluoro-resin emulsion is in 5 μ m, is preferably in 2 μ m, more preferably in 0.5 μ m.
As optimal technical scheme, the described inorganic filler of step of the present invention (1) is the mixture of any one or at least two kinds in silica, aluminium oxide, aluminium nitride, boron nitride, titanium dioxide, barium titanate, barium sulfate, talcum powder, aluminium hydroxide, lithopone, calcium carbonate, wollastonite, kaolin, shepardite, diatomite, bentonite, silicon powder or ground pumice, the mixture that is preferably any one or at least two kinds in silica, titanium dioxide or barium titanate, more preferably silica is or/and titanium dioxide.
Preferably, the particle diameter of described inorganic filler is in 20 μ m, is preferably in 10 μ m, more preferably in 5 μ m.
As optimal technical scheme, the described base material that can be release of step of the present invention (2) is any one in polyimides, PEI, polyether-ether-ketone, Copper Foil or aluminium foil.
As optimal technical scheme, the described baking temperature of step of the present invention (3) is 100-400 ℃, is preferably 200-380 ℃, more preferably 250-380 ℃.
Preferably, described baking time is 1-60min, is preferably 10-60min.
Preferably, described resin layer thickness is 1-400 μ m, is preferably 5-350 μ m, more preferably 10-300 μ m.
As optimal technical scheme, the temperature of the described high temperature lamination of step of the present invention (4) sintering is 340-400 ℃, is preferably 350-390 ℃, more preferably 380 ℃.
Preferably, the time of described sintering is 0.5-4 hour, is preferably 0.5-2.5 hour, more preferably 1-2 hour.
Second aspect, the present invention also provides a kind of microwave circuit PTFE composite medium substrate, and described substrate adopts the method preparation as described in first aspect present invention.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention, by introduce thickener in fluororesin system, makes the viscosity of dispersion liquid controlled, is convenient to coating molding;
(2) the present invention, by the method for coating molding, makes the thickness of substrate conveniently adjusted;
(3) the present invention can make the composite base plate that high filler is filled, and is suitable for mass large-scale production;
(4) the PTFE composite medium substrate even thickness that the present invention obtains, does not lump and reunites, excellent combination property.
The specific embodiment
Technological means and the effect thereof for further setting forth the present invention, taked, be described in detail explanation, but the present invention is not confined in scope of embodiments below in conjunction with the preferred embodiments of the present invention.
Embodiment 1
PTFE resin emulsion, particle diameter 0.25 μ m, resin content 55wt%, Daikin company produces, the trade mark: D210C.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525.
Thickener: polyoxyethylene groups distyrene phenyl ether, Kao Corp, trade mark EMULGEN A-60.
Get above-mentioned PTFE resin emulsion 454.5g, add 250g silicon powder, thickener 4.0g, carries out high-speed stirred and mixes 2h, and the viscosity of test glue is 420mPa.s, and viscosity is in normal range (NR).
Above-mentioned glue is coated on copper foil surface with coating machine, and coating thickness is the resin bed of 255 μ m, obtains adhesive coated foil.
Adhesive coated foil is placed in to the vacuum drying oven of 100 ℃, baking 1h, removes minute water, toasts 1h and remove organic additive at 250 ℃, at 350 ℃, toasts 10min, resin bed and Copper Foil is peeled off after cooling, obtains the resin bed of thickness homogeneous good-looking.
For making the sheet material that 1.0mm is thick, 4 thick PTFE resin beds of 255 μ m are carried out superimposed, size is 250 * 250mm, at the thick Copper Foil of the upper and lower surface covering 1OZ of superimposed good resin bed, carry out lamination, about 300-500PSI exerts pressure, maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Embodiment 2
PTFE resin emulsion, particle diameter 0.25 μ m, resin content 55wt%, Daikin company produces, the trade mark: D210C.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525.
Thickener: polyoxyethylene groups distyrene phenyl ether, Kao Corp, trade mark EMULGEN A-60.
Get above-mentioned PTFE resin emulsion 454.5g, add 250g silicon powder, thickener 4.0g, carries out high-speed stirred and mixes 2h, and the viscosity of test glue is 420mPa.s, and viscosity is in normal range (NR).
Above-mentioned glue is coated on copper foil surface with coating machine, and coating thickness is the resin bed of 104 μ m, obtains adhesive coated foil.
Adhesive coated foil is placed in to the vacuum drying oven of 100 ℃, baking 1h, removes minute water, toasts 1h and remove organic additive at 250 ℃, at 350 ℃, toasts 10min, resin bed and Copper Foil is peeled off after cooling, obtains the resin bed of thickness homogeneous good-looking.
For making the sheet material that 1.0mm is thick, 10 thick PTFE resin beds of 104 μ m are carried out superimposed, size is 250 * 250mm, at the thick Copper Foil of the upper and lower surface covering 1OZ of superimposed good resin bed, carry out lamination, about 300-500PSI exerts pressure, maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Embodiment 3
PTFE resin emulsion, particle diameter 0.25 μ m, resin content 55wt%, Daikin company produces, the trade mark: D210C.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525; Titanium dioxide, particle diameter approximately 0.25 μ m, U.S. Huntsman Corporation, the trade mark: TR-28.
Thickener: polyoxyethylene groups distyrene phenyl ether, Kao Corp, trade mark EMULGEN A-60.
Get above-mentioned PTFE resin emulsion 318g, interpolation 60g silicon powder, 265g titanium dioxide, 5.2g thickener carry out high-speed stirred and mix 2h, and the viscosity of test glue is 550mPa.s, and viscosity is in normal range (NR).
Above-mentioned glue is coated on copper foil surface with coating machine, and coating thickness is the resin bed of 206 μ m, obtains adhesive coated foil.
Adhesive coated foil is placed in to the vacuum drying oven of 100 ℃, baking 1h, removes minute water, toasts 1h and remove organic additive at 250 ℃, at 350 ℃, toasts 10min, resin bed and Copper Foil is peeled off after cooling, obtains the resin bed of thickness homogeneous good-looking.
For making the sheet material that 1.0mm is thick, 5 thick PTFE resin beds of 206 μ m are carried out superimposed, size is 250 * 250mm, at the thick Copper Foil of the upper and lower surface covering 1OZ of superimposed good resin bed, carry out lamination, about 300-500PSI exerts pressure, maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Embodiment 4,
Tetrafluoroethene-perfluorinated alkoxy vinyl ether resin emulsion, particle diameter 0.30 μ m, resin content 80wt%, Daikin company produces, the trade mark: ND-110.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525.
Titanium dioxide, particle diameter approximately 0.25 μ m, U.S. Huntsman Corporation, the trade mark: TR-28.
Thickener: NPE, Jiangsu Hai'an Petrochemical Plant, the trade mark: TX-4
Get above-mentioned tetrafluoroethene-perfluorinated alkoxy vinyl ether resin emulsion 219g, add 60g silicon powder, 265g titanium dioxide, thickener 1.5g, carry out high-speed stirred and mix 1.5h, and the viscosity of test glue is 150mPa.s, and viscosity is in normal range (NR).
Above-mentioned glue is coated on copper foil surface with coating machine, and coating thickness is the resin bed of 55 μ m, obtains adhesive coated foil.
Adhesive coated foil is placed in to the vacuum drying oven of 100 ℃, baking 1h, removes minute water, toasts 1h and remove organic additive at 250 ℃, at 350 ℃, toasts 10min, resin bed and Copper Foil is peeled off after cooling, obtains the resin bed of thickness homogeneous good-looking.
For making the sheet material that 0.2mm is thick, 4 thick PTFE resin beds of 55 μ m are carried out superimposed, size is 250 * 250mm, at the thick Copper Foil of the upper and lower surface covering 1OZ of superimposed good resin bed, carry out lamination, about 300-500PSI exerts pressure, maximum temperature and retention time are 380 ℃/60min, obtain the copper-clad plate of tetrafluoroethene-perfluorinated alkoxy vinyl ether.
Embodiment 5,
PTFE resin emulsion, particle diameter 0.25 μ m, resin content 55wt%, Daikin company produces, the trade mark: D210C.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525; Titanium dioxide, particle diameter approximately 0.25 μ m, U.S. Huntsman Corporation, the trade mark: TR-28.
Thickener: neopelex, Wanrong, Suzhou Chemical Industry Science Co., Ltd, trade mark WR-LAS60.
Get above-mentioned PTFE resin emulsion 318g, interpolation 60g silicon powder, 265g titanium dioxide, 7.8g thickener carry out high-speed stirred and mix 2h, and the viscosity of test glue is 800mPa.s, and viscosity is in normal range (NR).
Above-mentioned glue is coated on copper foil surface with coating machine, and coating thickness is the resin bed of 206 μ m, obtains adhesive coated foil.
Adhesive coated foil is placed in to the vacuum drying oven of 100 ℃, baking 1h, removes minute water, toasts 1h and remove organic additive at 250 ℃, at 350 ℃, toasts 10min, resin bed and Copper Foil is peeled off after cooling, obtains the resin bed of thickness homogeneous good-looking.
For making the sheet material that 1.0mm is thick, 5 thick PTFE resin beds of 206 μ m are carried out superimposed, size is 250 * 250mm, at the thick Copper Foil of the upper and lower surface covering 1OZ of superimposed good resin bed, carry out lamination, about 300-500PSI exerts pressure, maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Comparative example 1
Suspended PTFE resin powder, particle diameter approximately 35 μ m, Daikin company produces.
Fluororesin dispersion emulsion proportion of composing: PTFE emulsion 100g, PFA emulsion 10g, FEP emulsion 10g, appropriate amount of deionized water, is adjusted to 50% by solid content.Emulsion is all Daikin company and produces.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525.
Lubricant: DPG (DPG), commercially available.
Get above-mentioned PTFE toner 500g, add 500g silicon powder, in high-speed mixer, be uniformly mixed about 1h, add again the lubricant DPG of 200g, mix at a slow speed 20min, by mixture, send extruder, be extruded into the bar of diameter 5mm, this bar repeatedly rolls again, finally obtains the sheet material of 250 * 250 * 1.0mm specification.
This sheet material is carried out to 300 ℃/120min heat treatment, cooling after, immerse 3-5min in above-mentioned fluororesin dispersion emulsion, after taking-up, putting into baking oven is dried successively, cures and sintering, be dried, cure with sintering condition and be followed successively by: 100 ℃/10min, 300 ℃/10min, 380 ℃/10min.The both sides of gained substrate cover the thick Copper Foil of 1OZ and carry out lamination, the about 300-500PSI that exerts pressure, and maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Comparative example 2
Suspended PTFE resin powder, particle diameter approximately 35 μ m, Daikin company produces.
Fluororesin dispersion emulsion proportion of composing: PTFE emulsion 100g, PFA emulsion 10g, FEP emulsion 10g, appropriate amount of deionized water, is adjusted to 50% by solid content.Emulsion is all Daikin company and produces.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525; Titanium dioxide, particle diameter approximately 0.25 μ m, U.S. Huntsman Corporation, the trade mark: TR-28.
Lubricant: DPG (DPG), commercially available.
Get above-mentioned PTFE toner 350g, add 120g silicon powder and 530g titanium dioxide, in high-speed mixer, be uniformly mixed about 1h, add again the lubricant DPG of 300g, mix at a slow speed 20min, by mixture, send extruder, be extruded into the bar of diameter 5mm, this bar repeatedly rolls again, finally obtains the sheet material of 250 * 250 * 1.0mm specification.
This sheet material is carried out to heat treatment in 300 ℃/120 minutes, cooling after, immerse 3-5min in above-mentioned fluororesin dispersion emulsion, after taking-up, putting into baking oven is dried successively, cures and sintering, be dried, cure with sintering condition and be followed successively by: 100 ℃/10min, 300 ℃/10min, 380 ℃/10min.The both sides of gained substrate cover the thick Copper Foil of 1OZ and carry out lamination, the about 300-500PSI that exerts pressure, and maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Comparative example 3
PTFE resin emulsion, particle diameter 0.25 μ m, resin content 55wt%, Daikin company produces, the trade mark: D210C.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525.
Thickener: polyoxyethylene groups distyrene phenyl ether, Kao Corp, trade mark EMULGEN A-60.
Get above-mentioned PTFE resin emulsion 454.5g, add 250g silicon powder, thickener 0.8g, carries out high-speed stirred and mixes 2h, and the viscosity of test glue is 95mPa.s, and viscosity is on the low side.
Above-mentioned glue is coated on copper foil surface with coating machine, and coating thickness is the resin bed of 255 μ m, obtains adhesive coated foil.
Adhesive coated foil is placed in to the vacuum drying oven of 100 ℃, baking 1h, removes minute water, toasts 1h and remove organic additive at 250 ℃, at 350 ℃, toasts 10min, resin bed and Copper Foil is peeled off after cooling, obtains the resin bed of thickness homogeneous good-looking.
For making the sheet material that 1.0mm is thick, 4 thick PTFE resin beds of 255 μ m are carried out superimposed, size is 250 * 250mm, at the thick Copper Foil of the upper and lower surface covering 1OZ of superimposed good resin bed, carry out lamination, about 300-500PSI exerts pressure, maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Comparative example 4
PTFE resin emulsion, particle diameter 0.25 μ m, resin content 55wt%, Daikin company produces, the trade mark: D210C.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525.
Thickener: polyoxyethylene groups distyrene phenyl ether, Kao Corp, trade mark EMULGEN A-60.
Get above-mentioned PTFE resin emulsion 454.5g, add 250g silicon powder, thickener 7.5g, carries out high-speed stirred and mixes 2h, and the viscosity of test glue is 880mPa.s, and viscosity is higher.
Above-mentioned glue is coated on copper foil surface with coating machine, and coating thickness is the resin bed of 255 μ m, obtains adhesive coated foil.
Adhesive coated foil is placed in to the vacuum drying oven of 100 ℃, baking 1h, removes minute water, toasts 1h and remove organic additive at 250 ℃, at 350 ℃, toasts 10min, resin bed and Copper Foil is peeled off after cooling, obtains the resin bed of thickness homogeneous good-looking.
For making the sheet material that 1.0mm is thick, 4 thick PTFE resin beds of 255 μ m are carried out superimposed, size is 250 * 250mm, at the thick Copper Foil of the upper and lower surface covering 1OZ of superimposed good resin bed, carry out lamination, about 300-500PSI exerts pressure, maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Comparative example 5
PTFE resin emulsion, particle diameter 0.25 μ m, resin content 55wt%, Daikin company produces, the trade mark: D210C.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525; Titanium dioxide, particle diameter approximately 0.25 μ m, U.S. Huntsman Corporation, the trade mark: TR-28.
Thickener: polyoxyethylene groups distyrene phenyl ether, Kao Corp, trade mark EMULGEN A-60.
Get above-mentioned PTFE resin emulsion 318g, interpolation 60g silicon powder, 265g titanium dioxide, 0.75g thickener carry out high-speed stirred and mix 2h, and the viscosity of test glue is 85mPa.s, and viscosity is on the low side.
Above-mentioned glue is coated on copper foil surface with coating machine, and coating thickness is the resin bed of 206 μ m, obtains adhesive coated foil.
Adhesive coated foil is placed in to the vacuum drying oven of 100 ℃, baking 1h, removes minute water, toasts 1h and remove organic additive at 250 ℃, at 350 ℃, toasts 10min, resin bed and Copper Foil is peeled off after cooling, obtains the resin bed of thickness homogeneous good-looking.
For making the sheet material that 1.0mm is thick, 5 thick PTFE resin beds of 206 μ m are carried out superimposed, size is 250 * 250mm, at the thick Copper Foil of the upper and lower surface covering 1OZ of superimposed good resin bed, carry out lamination, about 300-500PSI exerts pressure, maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Comparative example 6
PTFE resin emulsion, particle diameter 0.25 μ m, resin content 55wt%, Daikin company produces, the trade mark: D210C.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525; Titanium dioxide, particle diameter approximately 0.25 μ m, U.S. Huntsman Corporation, the trade mark: TR-28.
Thickener: polyoxyethylene groups distyrene phenyl ether, Kao Corp, trade mark EMULGEN A-60.
Get above-mentioned PTFE resin emulsion 318g, interpolation 60g silicon powder, 265g titanium dioxide, 8.0g thickener carry out high-speed stirred and mix 2h, and the viscosity of test glue is 900mPa.s, and viscosity is higher.
Above-mentioned glue is coated on copper foil surface with coating machine, and coating thickness is the resin bed of 206 μ m, obtains adhesive coated foil.
Adhesive coated foil is placed in to the vacuum drying oven of 100 ℃, baking 1h, removes minute water, toasts 1h and remove organic additive at 250 ℃, at 350 ℃, toasts 10min, resin bed and Copper Foil is peeled off after cooling, obtains the resin bed of thickness homogeneous good-looking.
For making the sheet material that 1.0mm is thick, 5 thick PTFE resin beds of 206 μ m are carried out superimposed, size is 250 * 250mm, at the thick Copper Foil of the upper and lower surface covering 1OZ of superimposed good resin bed, carry out lamination, about 300-500PSI exerts pressure, maximum temperature and retention time are 380 ℃/60min, obtain PTFE copper-clad plate.
Comparative example 7
PTFE resin emulsion, particle diameter 0.25 μ m, resin content 55wt%, Daikin company produces, the trade mark: D210C.
Inorganic filler: silicon powder, particle diameter approximately 1.5 μ m, Co., Ltd of Xi Bi section, the trade mark: MEGASIL525; Titanium dioxide, particle diameter approximately 0.25 μ m, U.S. Huntsman Corporation, the trade mark: TR-28.
Get above-mentioned PTFE resin emulsion 318g, interpolation 60g silicon powder, 265g titanium dioxide carry out high-speed stirred and mix 2h, and the viscosity of test glue is 50mPa.s, and viscosity is too low.
Above-mentioned glue is coated on copper foil surface with coating machine, due to viscosity is too low cannot moulding, can not obtain can the actual resin coated copper foil using.
For the copper-clad plate of above-described embodiment 1-5 and comparative example 1-7 making, test the performances such as its dielectric constant (Dk), dielectric loss (Df), peel strength and water absorption rate and breakdown voltage.Test result is as shown in table 1.
Table 1
Above performance test methods is as follows:
Dielectric constant (Dk), dielectric loss (Df): IPC-TM-650 2.5.5.9 method is used in test;
Water absorption rate: IPC-TM-650 2.6.2.1 method is used in test;
Breakdown voltage: IPC-TM-650 2.5.6 method;
Peel strength: IPC-TM-650 2.4.8 method is used in test.
Known by embodiment 1-2, by the collocation of different resin layer thickness, all can obtain the copper-clad plate of 1.0mm thickness; From table 1, each performance parameter can draw, as long as formula is the same, the arrange in pairs or groups performance of prepared PTFE composite medium substrate of different-thickness is close.
By example 3 and 4, change fluoro-resin emulsion and can make the composite medium substrate that combination property is close equally.
Known by embodiment 3 and 5, fill a prescription when identical, change different thickeners, as long as viscosity, in reasonable interval, can make the PTFE composite medium substrate of excellent combination property.
By embodiment 1, compared and can find out with comparative example 1-2, the PTFE composite medium substrate water absorption rate that embodiment 1 makes is low, and breakdown voltage is high, excellent combination property.
By embodiment 1, compare with comparative example 3-4 and embodiment 3 compares and can find out with comparative example 5-6, the viscosity of glue is very big on the impact of copper-clad plate, when the viscosity of glue all can cause applying when lower than 100mPa.s or higher than 850mPa.s, resin layer thickness is inhomogeneous, thereby have influence on the performance of copper-clad plate, especially breakdown voltage is had the greatest impact, embodiment 1 and 3 breakdown voltage are apparently higher than comparative example 3-6.
Known by comparative example 7, owing to not adding thickener, the viscosity of glue is too low, cannot coating molding, fail to make corresponding PTFE composite medium substrate.
Performance parameter from the prepared PTFE composite medium substrate of above-described embodiment 1-5, with respect to prior art, preparation method of the present invention can obtain the PTFE composite medium substrate of the convenient adjusting of thickness and excellent performance, and this preparation method's simple process, prepared copper-clad plate excellent combination property, and sheet metal thickness is convenient to regulate, is beneficial to large-scale industrialization and produces.
Certainly, the embodiment of the above, is preferred embodiments of the present invention, is not used for limiting practical range of the present invention, the equivalence of doing according to structure, feature and principle described in the present patent application the scope of the claims therefore all changes or modifies, and is included in the present patent application the scope of the claims.
Claims (10)
1. a preparation method for PTFE composite medium substrate for microwave circuit, is characterized in that, described method comprises the steps:
(1) fluoro-resin emulsion, inorganic filler are proportionally carried out to mixed at high speed, prepare fluororesin dispersion liquid, adjust the viscosity of dispersion liquid at 100mPa.s-850mPa.s;
(2) by dispersion liquid step (1) Suo Shu with coating equipment be coated in can be release base material on, obtain the base material of resinizing of even thickness;
(3) base material of resinizing step (2) Suo Shu is toasted, after baking, resin bed and base material are carried out release separatedly, obtain the resin bed of even thickness;
(4) by resin bed step (3) Suo Shu according to the thickness of substrate and size, carry out cutting and superimposed, then on the two sides of resin bed, be covered with Copper Foil and carry out high temperature lamination sintering, can obtain the PTFE composite medium substrate of two-sided copper foil covered.
2. the method for claim 1, is characterized in that, the viscosity of the described dispersion liquid of step (1) is 150mPa.s-850mPa.s, more preferably 300mPa.s-600mPa.s.
3. method as claimed in claim 1 or 2, is characterized in that, step (1) is adjusted the viscosity of dispersion liquid by adding thickener.
4. method as claimed in claim 3, it is characterized in that, the described thickener of step (1) is the mixture of any one or at least two kinds in polyoxyethylene groups distyrene phenyl ether, neopelex, NPE, lauryl sodium sulfate or poly dimethyl silane, is preferably polyoxyethylene groups distyrene phenyl ether or NPE.
5. the method as described in claim 1-4 any one, it is characterized in that, the described fluoro-resin emulsion of step (1) is the mixture of any one or at least two kinds in polyflon emulsion, tetrafluoroethene-perfluorinated alkoxy vinyl ether resin emulsion or fluorinated ethylene propylene copolymer resin emulsion, is preferably polyflon emulsion;
Preferably, the particle diameter of described fluoro-resin emulsion is in 5 μ m, is preferably in 2 μ m, more preferably in 0.5 μ m.
6. the method as described in claim 1-5 any one, it is characterized in that, the described inorganic filler of step (1) is the mixture of any one or at least two kinds in silica, aluminium oxide, aluminium nitride, boron nitride, titanium dioxide, barium sulfate, barium titanate, talcum powder, aluminium hydroxide, lithopone, calcium carbonate, wollastonite, kaolin, shepardite, diatomite, bentonite, silicon powder or ground pumice, the mixture that is preferably any one or at least two kinds in silica, titanium dioxide or barium titanate, more preferably silica is or/and titanium dioxide;
Preferably, the particle diameter of described inorganic filler is in 20 μ m, is preferably in 10 μ m, more preferably in 5 μ m.
7. the method as described in claim 1-6 any one, is characterized in that, the described base material that can be release of step (2) is any one in polyimides, PEI, polyether-ether-ketone, Copper Foil or aluminium foil.
8. the method as described in claim 1-7 any one, is characterized in that, the described baking temperature of step (3) is 100-400 ℃, is preferably 200-380 ℃, more preferably 250-380 ℃;
Preferably, described baking time is 1-60min, is preferably 10-60min;
Preferably, described resin layer thickness is 1-400 μ m, is preferably 5-350 μ m, more preferably 10-300 μ m.
9. the method as described in claim 1-8 any one, is characterized in that, the temperature of the described high temperature lamination of step (4) sintering is 340-400 ℃, is preferably 350-390 ℃, more preferably 380 ℃;
Preferably, the time of described sintering is 0.5-4 hour, is preferably 0.5-2.5 hour, more preferably 1-2 hour.
10. a microwave circuit PTFE composite medium substrate, is characterized in that, adopts the method preparation described in claim 1-9 any one.
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| CN104647868A (en) * | 2015-02-10 | 2015-05-27 | 郴州功田电子陶瓷技术有限公司 | Manufacturing method for polytetrafluoroethylene copper-clad plate |
| CN106188998A (en) * | 2016-07-12 | 2016-12-07 | 刘世超 | A kind of PTFE medium substrate high-frequency copper-clad plate |
| CN107641276A (en) * | 2017-07-17 | 2018-01-30 | 常州中英科技股份有限公司 | One kind is without fibre-reinforced fluorine resin base copper-clad plate and preparation method thereof |
| CN108456387A (en) * | 2017-12-28 | 2018-08-28 | 浙江华正新材料股份有限公司 | A kind of no glass type polytetrafluoroethylene (PTFE) film, production method and its application |
| CN111114069A (en) * | 2019-12-23 | 2020-05-08 | 武汉理工大学 | Ceramic/polytetrafluoroethylene composite medium substrate and preparation method thereof |
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| CN115594512A (en) * | 2021-07-08 | 2023-01-13 | 清华大学（Cn） | PTFE (polytetrafluoroethylene) -ceramic slurry for high-frequency microwaves, sintered film of PTFE-ceramic slurry, and preparation methods and applications of PTFE-ceramic slurry and sintered film |
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| CN104647868B (en) * | 2015-02-10 | 2017-09-08 | 郴州功田电子陶瓷技术有限公司 | A kind of preparation method of Copper Clad Laminates Based On Polytetrafluoroethylene |
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| CN107641276A (en) * | 2017-07-17 | 2018-01-30 | 常州中英科技股份有限公司 | One kind is without fibre-reinforced fluorine resin base copper-clad plate and preparation method thereof |
| CN108456387A (en) * | 2017-12-28 | 2018-08-28 | 浙江华正新材料股份有限公司 | A kind of no glass type polytetrafluoroethylene (PTFE) film, production method and its application |
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| CN111114069A (en) * | 2019-12-23 | 2020-05-08 | 武汉理工大学 | Ceramic/polytetrafluoroethylene composite medium substrate and preparation method thereof |
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| CN113845740A (en) * | 2020-06-11 | 2021-12-28 | 四川大学 | Preparation method of high-thermal-conductivity polytetrafluoroethylene composite film material |
| CN113845740B (en) * | 2020-06-11 | 2023-03-21 | 四川大学 | Preparation method of high-thermal-conductivity polytetrafluoroethylene composite film material |
| CN115594512A (en) * | 2021-07-08 | 2023-01-13 | 清华大学（Cn） | PTFE (polytetrafluoroethylene) -ceramic slurry for high-frequency microwaves, sintered film of PTFE-ceramic slurry, and preparation methods and applications of PTFE-ceramic slurry and sintered film |
| CN115594512B (en) * | 2021-07-08 | 2023-05-30 | 清华大学 | PTFE-ceramic slurry for high-frequency microwaves and sintering film thereof, and preparation method and application thereof |
| CN114045072A (en) * | 2021-12-06 | 2022-02-15 | 中国电子科技集团公司第四十六研究所 | Method suitable for adjusting viscosity of PTFE composite slurry |
| CN115820154A (en) * | 2022-12-07 | 2023-03-21 | 广东生益科技股份有限公司 | Glue-coated copper foil for capacitor burying and preparation method and application thereof |
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